Conformational Dynamics of the Pyrene Excimer

The conformational dynamics of the pyrene excimer play a critical role in its unique fluorescence properties. Yet, the influence of multiple local minima on its excited-state behavior remains underexplored. Using a combination of time-dependent density functional theory (TD-DFT) and unsupervised machine learning analysis, we have identified and characterized a diverse set of stable excimer geometries in the first excited state. Our analysis reveals that rapid structural reorganization towards the most stable stacked-twisted conformer dominates the excimer’s photophysics, outcompeting radiative relaxation. This conformer, which is primarily responsible for the characteristic red-shifted, structureless fluorescence emission, reconciles experimental observations of long fluorescence lifetimes and emission profiles. These findings provide new insights into the excited-state dynamics of excimers. They may inform the design of excimer-based materials in fields ranging from organic electronics to molecular sensing.